Vinyl polymer compositions containing as a plasticizer an ester of a pentaerythritolhydroxyalkyl ether



ritol, and technical mixtures of the same.

Patented Dec. 18, 1951 VINYL POLYMER COMPOSITIONS CONTAIN- ING AS APLASTICIZER AN ESTER OF A PENTAERYTHRITOL HYDROXYALKYL ETHER Christy J.Vander Valk, Clifton, N. J assignor to Heyden Chemical Corporation, NewYork, N. 'if., a corporation of Delaware No Drawing. Application August18, 1948,

Serial No. 44,988

11 Claims. (Cl. 260-3L4) My invention relates particularly to vinylresin compositions capable of being used for many difierent purposes,but which are especially appli-- -cable where a great degree offlexibility is desired at low temperatures, also where a high tensilestrength is desired.

An object of my invention is to obtain vinyl resin or polymercompositions, plasticized by the presence of an ester of a hydroxyalkylether of one of the pentaerythritols, by which I mean pentaerythritol,dipentaerythritol, tripentaeryth- These plasticizers are found to impartthereto an exceptionally good flexibility at low temperatures as well asa higher tensile strength. For example vinyl resin films containing suchplasticizers as, for instance, propionates or butyrates ofpentaerythritol tetrahydroxyalkyl ethers, display low temperatureflexibility as well as tensile strength superior to that which has beenobtained with films plasticized by the more commonly used plasticizers,while the other properties obtained are at least as good. Furtherobjects will appear from the detailed description hereinafter.

While my invention is capable of embodiment in many different forms, byway of illustration I have described hereinafter only certainembodiments thereof.

This invention is concerned, for instance, with the preparation of vinylresin compositions which may contain by weight approximately 67.2 parts,

2 for instance as tetrabutyrate or tetrapropiona of thetetrahydroxyethyl or tetrahydroxypropyl ether or pentaerythritol, whichserve as the plasticizer.

As more specifically exemplifying my invention, and the comparativeproperties of the plasticized products thus obtained: Vinyl polymercompositions-were prepared in each of the following examples by mixingin a Banbury mixer, by weight, 67.2 parts of a vinyl-acetate-vinylchloride copolymer, containing 90% thereof as vinyl chloride, 30 partsof the particular plasticizer hereinafter mentioned, 1.05 parts ofcarnauba wax as a lubricant, and 1.75 parts of basic lead carbonate as astabilizer. The milled mass was transferred to mixing rolls maintainedat 240-300 F., depending upon the plasticity of the batch, milled forapproximately 10 minutes-and then sheeted. The sheets were cut to 5.5inch squares and molded at 295 F. and 800 p. s. i. for 10 minutes. Thelow temperature flexibility of the molded sheets was determined as thetemperature C.) at which a 1.5 x 0.5 inch sample, which had been cooleduntil rigid in a Dry Ice-alcohol bath, regained its flexibility. Theother properties reported were determined by standard test methods. Ihave found, also, that all the plasticizers in the following table werecompatible with the vinyl poylmer or resin over the range from 10 toparts, or per cent, of the plasticizer, as compared with the vinylpolymer or resin.

The results of a series of tests follows, in a tabulation in which PE isused to signify pentaerythritol. All of the esters referred to in saidtabulation were made from technical pentaerythritol, although any otherpentaerythritol, dipentaerythritalor tripentaerythritol can be usedtherein.

Volatility Low Room Shore Ultimate Exzlim- Pmflcim Temp, Temp, HardnessTensile fir g rg' P e Flex. Flex. 15 seconds m. Y

A..." PE Tetrapropionate having the structural formula: 6 5. 6 1, 713fair.

C(CHzOOCCH2CHs)| B Tetraacetate of PE tetrahydroxyethyl ether having thestructuralformula: -8 4. 9 84 2,870 good.

C(CHzOCHrCHzOOCCH C.-- Tet propionate of PE tetrahydroxyethyl etherhaving the structural for- -12 4.9 90 3,120 Do.

in a: C(CHZOCHZCH1OOCCH2CH3)4, D... Tetrabutyrate of PEtetrahydroxyethyl ether having the structural formula: 25 5.3 76 2, 250D0.

C(CHzOCH2CH2OOCCH2CH2CH3)4. E. 'Ietraacetate of PE tetrahydmxypropylether having the structural formula: --11 4. 9 87 3,160 Do.

C(CHzOCHzCHgCHzOOCCHaN. F..-" Tetrapropionate of PE tetrahydroxypropylether having the structural forl7 4.9 85 3, 320 Do.

mula: (CHzOCHZCHzCHzOOCCHzCHi). G.. Tetrabutyraie of PEtetrahydroxypropyl ether having the structural for- --24 4.9 87 2,720Do.

mule: C(CHzOCH2CHzCHzOOCCH2CH1CHI)|- See references at bottom of table.

Volatility Low Room Shore Ultimate Exam Plasticlzer Temp. Temp. HardnessTensile f fi gg p18 Flex. Flex. seconds lb./ln.'- a

at 105 C H..." Tripropionate of PE monoacetate trihydroxy ropyl etherhaving the struc' 4. 2 6. l 84 2, 630 lair.

tural formula: CHaCO0CHzC(CHz0CH1 HzCHzOOCQHzCHah. I v 1.- Tributyrateof PE mononcetate tribydrox prolgyl ether having the structural 8. 7 5.2 86 2, 530 good. formula: CHaCOOCHaCKCHzOCHzC 2C OCCH2CH2CH5)3. JTripropionate of PE monopropionatc trih droxyethyl ether having the 12.9 5. 3 82 2,270 D0.

structural formula: CH:CHzCOOCH2C( HzQCHzCHzOOCCHaCHah. K..."Tributyrate of PE monoprogionatc trih droxycthyl ether having the struc-19.3 5. 3 82 2,270 Do.

tural ormula: CHZOHIC 0011:0(0 2OCH2CH200CCH2CH2CH:)3. L.-." Flexol OPl7 5.0 70 1,956 Do. M. Flexol DOP-S4jPial l2 5. l 80 2, 393 D0.

Flexol DOP is manufactured by, ture, for instance Plasticizer Chart di-2ethylhexylpbthalate.

Flexol DOP Special is merely an improved Flexol DOP.

The plasticizers which are found to give the most satisfactory resultsare the tetrapropionates and the tetrabutyrates of pentaerythritoltetrao hydroxyethyl ether and pentaerythritol tetrahydroxypropyl ethers,as the esters of the lower fatty acids do not impart satisfactoryplasticity to the films, whereas the esters of the longer chain acids,such as the laurates, are not sufficiently compatible with the vinylpolymers. Better low temperature flexibility has been obtained with thebutyrates of the pentaerythritol tetrahydroxyalkyl ethers than with theesters of pentaerythritol octahydroxyalkyl ethers;

While I have described my invention above in detail, it is to beunderstood that many changes may be made therein without departing frommy invention. For instance, the proportions of the various constituentsof the compositions may be varied as desired.

I claim:

1. A vinyl chloride vinyl acetate copolymer resin containing aplasticizer consisting of a substituted pentaerythritol wherein each ofthe original hydroxyl groups of the pentaerythritol are replaced, threeof the original hydroxyl groups of each monopentaerythritol group beingreplaced. by an acylated hydroxyalkyl ether group the acyl 1 group beingderived from an aliphatic fatty acid having 2 to 4 carbon atoms and thelast remaining hydroxyl group of each monopentaerythritol group beingreplaced by an acyl group derived from an aliphatic fatty acidcontaining two to four carbon atoms.

2. A vinyl chloride vinyl acetate copolymer resin containing from 10 to50% by weight of a plasticizer consisting of a substitutedpentaerythritol wherein each of the original hydroxyl groups arereplaced, at least three of said original hydroxyl groups being eachreplaced by an acylated hydroxyalkyl ether group the acyl group beingderived from an aliphatic fatty acid having 2 to 4 carbon atoms and thelast remaining group being replaced by the acyl radical ,of propionicacid, said pentaerythritol being compatible with said resin andincluding in addition to the aforesaid plasticizer, a lubricant and astabilizer.

3. A vinyl chloride vinyl acetate copolymer resin containing from l0 to50% by weight of a plasticizer consisting of a substitutedpentaerythritol wherein each of the original hydroxyl groups or thepentaerythritol are each replaced by the propionic acid ester of ahydroxyalkyl ether.

4. A vinyl chloride vinyl acetate copolymer resin containing from 10 to50% by weight of a plasticizer consisting of a substitutedpentaerythritol wherein each of tne original hydroxyl groups of thepentaerythritol are each replaced by the butyric acid ester of ahydroxyalkyl ether.

5. A vinyl chloride vinyl acetate copolymer Carbide and Carbon Chemical;Corporation and has been disclosed in the literao. 4, Modern Plastics Encyclopedia, Modern Plastics Inc.,- New York, N, Y., 1947, as

resin containing a plasticizer consisting of a substitutedpentaerythritol wherein each of the original hydroxyl groups of thepentaerythritol ether, and the remaining hydroxyl group being consistingof acylated hydroxyalkyl ether and acyl, all of the acyl groups hereofbeing derived;

original hydroxyl groups of the pentaerythritol-- are replaced by anacylated hydroxyalkyl ether the acyl group thereof being derived from afatty group containing 2 to 4 carbon atoms.

7. A vinyl chloride vinyl acetate copolyme resin containing from 10' to50% by weight of a plasticizer consisting of. the tributyrate ester ofpentaerythritol monopropionate trihydroxyethyl ether, saidpentaerythritol being compatible with said resin and including inaddition to the aforesaid plasticizer, a lubricant and a stabilizer.

8. A vinyl chloride vinyl acetate copolymer resin containing from 10 to50% by weight of a plasticizer consisting of a substitutedpentaerythritol wherein each of the original hydroxyl groups ofthe-pentaerythritol are each replaced by the butyric acid ester of ahydroxyethyl ether.

9. \A vinyl chloride vinyl acetate copolymer resin containing from 10 to50% by weight of a plasticizer consisting of a substitutedpentaerythritol wherein each of the original hydroxyl 5 groups 6 thepentaerythritol are each replaced by the b tyric acid ester of ahydroxypropyl ether, said pentaerythritol being compatible with saidresin and including in addition to the aforesaid plasticiaer, alubricant and astabilizer.

10. A vinyl. chloride vinyl acetate copolymer resin containing from 10to 50% by weight of a plasticizer consisting of asubstituted'pe'nt-aerythritol wherein each oi the original hydroxylgroups of the pentaerythritol are each replaced by the propionic acidester of a hydr'oxyethyl ether, said pentaerythritol being compatiblewith said resin and including in addition to the aforesaid Plasticizer,a lubricant and a stabilizer.

11. A vinyl chloride vinyl acetate copolymer 70 resin containing from 10to 50% by weight of a plasticizer consisting of a substitutedpentaerythritol wherein each of the original hydroxyl groups of thepentaerythritol are each replaced by'the are replaced, at least three ofthe original hy-,. droxyl groups of each mono-pentaerythritol groupbeing replaced by an acylated hydroxyalkyl replaced by a radicalselected from the group acid having 2 to 4 carbon atoms and the etherresin and including in addition to the aforesaid UNITED STATES PATENTSplasticlzer, a, lubricant and.a stabilizer. Number Name Y Date CHRISTYJ- VANDER VALK- 1,922,459 Schmidt et a1. Aug. 15, 1933 REFERENCES CITED6 2,381,247 Barth et al Aug. 7, 1945 The following references are ofrecord in the file of this patent:

5. A VINYL CHLORIDE VINYL ACETATE COPOLYMER RESIN CONTAINING APLASTICIZER CONSISTING OF A SUBSTITUTED PENTAERYTHRITOL WHEREIN EACH OFTHE ORIGINAL HYDROXYL GROUPS OF THE PENTAERYTHRITOL ARE REPLACED, ATLEAST THREE OF THE ORIGINAL HYDROXYL GROUPS OF EACH MONO-PENTAERYTHRITOLGROUP BEING REPLACED BY AN ACYLATED HYDROXYALKYL ETHER, AND THEREMAINING HYDROXYL GROUP BEING REPLACED BY A RADICAL SELECTED FROM THEGROUP CONSISTING OF ACYLATED HYDROXYALKYL ETHER AND ACYL, ALL OF THEACYL GROUPS HEREOF BEING DERIVED FROM A FATTY ACID HAVING 2-4 CARBONATOMS AND THE ALKYL GROUP CONTAINING 2-4 CARBON ATOMS.